Study On Sulfonylation Of Carbon-Carbon σ-Bonds In Three-Membered/Four-Membered Carbocyclic Compounds

Carbocyclic compounds are a class of cyclic compounds composed of carbon atoms,which widely exist in various natural products and active molecules in nature,and various foods,medicines,materials,etc.,which play a huge role in human daily life,contain carbocyclic skeletons.The stability of carbocyclic compounds is greatly affected by the number of carbon atoms in its composition.Among them,three-membered and four-membered carbocyclic compounds have huge ring tension,are very unstable,and are prone to ring opening.The sulfonylation reaction of carbon-carbonσbond in carbocyclic compounds is mainly to react with various sulfonylation reagents or introduce external sulfur dioxide source to realize the sulfonylation of carbon-carbonσ-bond,which is often accompanied by carbocyclic ring-opening of the compound,and further obtain a more complex sulfone compound skeleton.In recent years,the ring-opening and carbon-carbonσbond sulfonylation reactions of carbocyclic compounds have been extensively reported,but most of them require high temperature,strong oxidants,strong acids,strong bases or toxic gases.In order to develop environmentally friendly ring-opening/sulfonylation reactions of carbocyclic compounds and expand the types of ring-opening/sulfonylation reactions of small molecule carbocyclic compounds,this thesis focuses on the sulfonylation reaction of carbon-carbonσ-bond of three-membered/quaternary-membered carbocyclic compounds is studied and will be illustrated from the following:（1）A silver-catalyzed ring-extending sulfonylation of vinylcyclopropanes with sodium sulfinate was achieved.In this reaction,silver nitrate is used as catalyst,and sodium sulfinate is used as sulfonyl source to realize the ring-extended sulfonylation of the carbon-carbonσ-bond in the three-membered ring,which provides a simple and effective way for the synthesis of1-sulfonylmethyl-3,4-dihydronaphthalene compounds,and enriches the synthesis methods of sulfone dihydronaphthalene skeletons.（2）A strategy was developed for the visible-light-catalyzed ring-opening/sulfonylation reaction of alkynoates with cyclic ketoxime esters via the insertion of an external sulfur source.In this sulfonylation transformation,the process of ring opening of cyclic ketoxime ester,insertion of sulfur dioxide,addition of carbon-carbon triple bond in alkynoate,intramolecular cyclization and 1,2-ester migration.A series of 3-cyanoalkylsulfonylcoumarin skeletons were synthesized in good yields,while providing a new idea for the sulfonylation of four-membered carbocyclic compounds.（3）A visible-light-catalyzed ring-opening/sulfonylation pathway of alkynyl indole and cyclic ketoxime ester was constructed.This strategy uses Na₂-Esion as the photocatalyst and K₂S₂O₅as an additional source of sulfur dioxide,which provides a green and efficient route for the synthesis of 2-cyanoalkylsulfonylpyrrolo[1,2-a]indole compounds.During this transformation,the cleavage of one carbon-carbonσ-bond and the generation of two new carbon-sulfur bonds and a new carbon-carbon bond are achieved.